10.1002/cctc.201901270
ChemCatChem
FULL PAPER
Vt – V>423 K
Yield of solketal, expressed in %, was calculated according to equation 6.
HI =
(Eq.2)
Vt
where Vt - total pore volume obtained from N2 adsorption measurements
and V>423 K relates to volume of water measured at temperature higher
than 423 K (in our measurements it was 673 K) and calculated using the
bulk liquid density for adsorbed water. According to applied definition,
material with HI = 1 is defined as highly hydrophobic, while this with HI =
0 shows hydrophilic nature.
S solketal Glycerol conv.
Y solketal
100
(Eq. 6)
Keywords: Glycerol ketalization, solketal formation, hierarchical
4. Catalytic reaction of glycerol ketalization
zeolites, a continuous flow system
The catalytic reaction of solketal synthesis was carried out under
atmospheric pressure at the temperature of 323 K in a continuous down-
flow reactor heated with an electric furnace (Fig. S3).The reactor was
loaded with a given amount of catalyst (0.5 g) with a glass wool as a bed
supporter. To avoid the clogging, the catalyst was mixed with an
amorphous silica in the weight ratio equal to 1 : 1. Both catalyst as well
as silica were fractioned to the same particle size (sieve fraction 0.3–0.5
mm). Catalysts were pre-activated at 623 K for 0.5 h in a helium flow
before catalytic run. The feed was a mixture of 4.8 ml of glycerol and
14.4 ml of acetone (corresponding to the molar ratio equal to 3 : 1 of
acetone : glycerol) dissolved in methanol (3.8 ml). In a typical run, the
feed containing acetone, glycerol and the additional solvent (methanol)
was pumped continuously into the reactor with flow rate equal to 6.4
cm3/h and WHSV equal to 3.4 h-1 (WHSV defined as the mass flow of
glycerol [kg/h])/(mass of catalyst [kg]). The experiments with WHSV in
the range of 3.4-8.4 h-1 have also been performed. The reaction products
were collected every 30 min. and analyzed by GC (VARIAN CP-3800)
equipped with a FID detector and a VF-5ms capillary column using
toluene as an internal standard. The glycerol conversion was defined as
the amount of converted glycerol divided by the amount of glycerol
before reaction and expressed in % according to equation 3.
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mol of glycerol converted
initial mol of glycerol
100
Glycerol conv.
(Eq. 3)
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mol of solketal formed
mol of glycerol converted
S solketal
100
(Eq. 4)
In addition to the solketal (2,2-dimethyl-1,3-dioxolane-4-methanol)
(Scheme 1, product 1a), small amount of undesired 6-membered ring
isomer (2,2-dimethyl-1,3-dioxan-5-ol) (Scheme 1, product 1b) was also
recorded. The selectivity to isomer, expressed in %, was calculated
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mol of isomer formed
mol of glycerol converted
S isomer
100
(Eq. 5)
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